Water-soluble disazo dyes



United States Patent Of 3,141,874 WATER-SOLUBLE DHSAZO DYES Hans llscher, Basel, and Carl Ryffel, Dornach, Switzerland, assignors to Sandoz Ltd., Basel, Switzerland No Drawing. Filed Get. 26, 1961, Ser. No. 147,725 Claims priority, application Switzerland Get. 28, 1960 7 flairns. (Cl. Zfi-dfil) This invention relates to Water-soluble disazo dyes of the formula A represents the radical of an azo component coupled in ortho-position to a hydroxy or amino group, which latter group may be substituted,

B a diphenyl radical which may be substituted,

D an acyl or heterocyclic radical which is free from reactive substituents, and in which the nucleus C may be further substituted.

The process for the production of the new dyes consists in reacting a water-soluble disazo dye of the formula wherein H2NBN=N- -NHD (In) with a hydroxy or aminonaphthalene which may be substituted, in such a manner that the diazo group enters into ortho position to the hydroxy or amino group.

In this specification and claims the expression reactive substituent refers to a substituent which is capable of forming a chemical linkage with cellulose and polyamide fibers that is stable to treatment with 50% aqueous pyridine solution (the so-called pyridine test).

The aminoazo dye of Formula II which is used as starting product is obtained by coupling the tetrazo compound of 1 mol of an unsubstituted or substituted 4,4- diamino-l,l'-diphenyl with 1 mol of a coupling component according tothe invention and with 1 mol of an aminobenzene which couples in para-position to the amino group and may be substituted if desired.

The following are named as examples of suitable coupling compounds of the naphthalene series based upon the radical A: hydroxynaphthalene-mono-, -dior -trisulfonic acids such as l-hydroxynaphthalene-4- or -5- sulfonic acid, 2-hydroXynaphthalene-4-, -6-, -7- or -8-sulfonic acid, 1-hydroXynaphthalene-3,6-, -4,6- -4,7- or -4,8-disulfonic acid, 2-hydroxynaphthalene-3,6- and -6,8-disulfonic acid, l-hydroxyand 2-hydroxynaphthalene-3,6,8- trisulfonic acid and their mixtures, 2-hydroxynaphthalene, 2-amino-8-hydroxynaphthalene-6-sulfonic acid which couples in acid solution, 2-arnino-8-hydroxynaphthalene-3,6- disulfonic acid, 2-(2',4,6-trimethyl)-phenylamino 8-hydroxynaphthalene-6-sulfonic acid, 2-aminonaphthalene-6- or -7-sulfonic acid and their N-methyl derivatives, acylamino hydroxynaphthalene-monoand -disulfonic acids, e.g. 2-acetylamino-5-hydroXynaphthalene-7-sulfonic acid, l-benzoylamino 8 hydroxynaphthalene 3,6-disulfonic acid, Z-N-carbomethoxyaminoor 2-N-carbethoxyamino- 3,141,874 Patented July 21, 1964 S-hydroxynaphthalene-1,7-disulfonic acid and 1,8-dihydroxynaphthalene-3,6-disulfonic acid.

Other suitable coupling components are e.g. l-hydroxy- 4-methylbenzene, 1-(2',5-dichloro) phenyl-3-methyl-5- pyrazolone-4-sulfonic acid, l-phenyl-3-methyl-5-pyrazolone, 1-(2'-chloro-6'-methyl) phenyl-B-methyl-S-pyrazolone, 1-phenyl-5-pyrazolone-3-ca.rboxylic acid, acetoacetylamino-benzene, l-acetoacetylamino 2,5 dimethoxybenzene, l-phenyl-3-methyl-5-pyrazolone-2,4 or -2',5'-disulfonic acid.

Important aminobenzenes which are based on the radical C are: aminobenzene, 1-amino-2- and -3-rnethylbenzene, 1-amino-3-acetylaminobenzene, 1-amino-2,5dimethoxybenzene, 1-amino-S-methyl-Z-methoxybenzene, lamino-3-propionyl and -butyrylaminobenzene, 1,3-diaminobenzene, l-amino-2,S-diniethylbenzene, 1-amino-2,3- tetramethylenbenzene.

Examples of suitable diamino compounds based upon the radical'B are: 4,4'-diamino-2,2'-dimethyl-l,1'-diphenyl, 4,4'-diamino-1,1-diphenyl, 4,4-diamino-2,2-dimethyl- 1,1-diphenyl-5-sulfonic acid, 4,4-diamino-2,2'-dimethyl- 1,1'-diphenyl-6-sulfonic acid, 4,4-diamino-3,3'-dimethyl= 1,1-diphenyl-6,6'-disulfonic acid, 4,4 diarnino l,l'diphenyl-2,2-disulfonic acid, 4,4'-diamino-1,1-diphenyl-3, 3-disulfonic acid, 4,4'-diamino-l,l-diphenyl-2,2', 5,5- tetrasulfonic acid, 4,4'-diamino-3,3-diethyl-1,l'-diphenyl 6,6'-'disulfonic acid, 4,4-diamino-3,3'-dirnethoXy-l,1-diphenyl-6,6'-disulfonic acid, 4,4-diamino-1,lf-diphenyl-3, 3'-dicarboxylic' acid, 4,4'-diamino-3,3'dimethoxy-l,1-diphenyl, 4,4-diami11o-3,3-dirnethyl-1,l'-diphenyl, 4,4'-diamino-l,1'-diphenyl-6,6'-sulfon-3,3 '-disulfonic acid.

The following are enumerated as examples'of functional derivatives of an organic acid suitable for use in the process: the halides, preferably the chlorides and bromides, and the anhydrides of substituted or unsubstituted fatty acids with 1 to 30 carbon atoms, e.g. acetyl chloride, acetic anhydride, maleic anhydride, isovaleric chloride, 2-ethylcaproic chloride, capric chloride, lauric chloride, oleic chloride, palmitic chloride, stearic anhydride and chloride, phenylacetic chloride, 2,4,S-trichlorophenoxyacetic chloride, the halides, preferably the chlorides and bromides, and the anhydrides of substituted or unsubstituted monoor di-valent arenecarboxylic acids, preferably of the benzene or naphthalene series, and of arylalkylor cycloalkyl-carboxylic acids, e.g. 4-tertiarybutylbenzoic chloride, butylglycoloxyacetic chloride, phenoxyand cresoxy-acetic chlorides, benzoic chloride, monoand dichlorobenzoic chlorides, cyclohexylcarboxylic chloride, the halides of alkanesulfonic acids with l to 30 carbon atoms, substituted or unsubstituted arenesulfonic acids, preferably of the benzene or naphthalene series, halogenoformic acid esters of substituted or unsubstituted aliphatic alcohols with 1 to 20 carbon atoms, of cycloaliphatic and arylaliphatic alcohols and of substituted or unsubstituted phenols and naphthols, e.g. the chloroformic acid esters of ethyl, amyl, hexyl, octyl, decyl, lauryl, cetyl, benzyl, or cyclohexyl alcohol, or of hydroxybenzene, 4- octylor 4-cyclohexyl-l-hydroxybenzene, ethyleneglycol monoethyl, butyl, heXyl, octyl, or phenyl ether, diethyleneglycol mono-methyl, -butyl or -phenyl ester.

Heterocyclic compounds which contain an exchangeable halogen atom are e.g. cyanuric chloride and bromide, primary and secondary condensation products of the cyanuric halides of the composition arenas a wherein y represents the radical, which may be further sub polyamide fibers from a Weakly alkaline to Weakly acid stituted, of a primary or secondary aliphatic, alicyclic, bath. They give bright, level shades of very good fastaromatic or heterocyclic amine, an aliphatic, alicyclic, ness to light, perspiration, washing, and alkaline and acid aromatic or heterocyclic hydroxy or thiol compound, but milling.

more Particularly thg radical of anilineiits alkyl and 1- In the following examples the parts and percentages are fonic acid or carboxylic acid derivatives, of low molecular by Weight and the temperatures in degrees centigrade. monoand di-alkyl amines, or the radical of ammonia E l 1 and 2 represents a halogen atom of a radical such as y, or xamp e 2,4,6-trichloropyrimidine or 2,4,6-tribromopyrimidine or 20 parts of the dye which is obtained by tetrazotization their derivatives which contain in the 5-position e.g. the of 4,4 diamino 5,5 dimethyl 1,1 diphenyl 2,2- following substituents: methyl, ethyl, carboxylic acid or disulfonic acid and coupling with l-amino-EB-methylbensulfonic acid amide which may be substituted on the zene and 1-hydroxynaphthalene-4-sulfonic acid, are disnitrogen atom, carboxylic acid methyl or ethyl ester, acyl, solved at 20 in 300 parts of water, 200 parts of acetone e.g. benzoyl, alkylene, e.g. allyl, chlorovinyl, substituted and parts of pyridine. In the course of 24 hours alkyl, e.g. carboxymethyl, chloro or bromomethyl, a 15 lauryl chloride is dropped in until the starting dye is no methylene group between two pyrimidine nuclei, 2,4,5,6- longer indicated in a chromatogram. During the contetrachloroor tetrabromo-pyrimidine, 2,6-dichloroor didensation reaction the pH value of the mixture is mainbromo-pyrimidine-4-carboxylic acid ethyl ester, 2,4,5-tritained at 6.5-7.0 by the addition of sodium bicarbonate.

chloropyrimidine, the 4- or S-carboxylic acid amide or The precipitated acylated dye is filtered off, washed with sulfonic acid amide derivatives of 2,6-dichloroor -dia little water and dried. An excess of lauric acid is bromo-pyrimidine which may be substituted on the nitroremoved by extraction. The dye dyes wool, silk and gen atom, 2,5,6-trichloro-4-methylpyrimidine, 2,4 dinylon in bright scarlet shades of very good light and chloro-5-chloromethyl-6-methylpyrimidine and 2,6 diwet fastness. chloro-4-trichloromethylpyrimidine. The method of dyeing is as follows: The bath is set When the introduced radicals of organic acids or of 25 at 40 with 500 parts of Water, 10 parts of anhydrous organic compounds contain substituents which can be sodium sulfate and 2 parts of the dye. 100 parts of readily split olf as anions or multiple linkages capable of wool fabri ar entered, and the bath i heated to 100 addition, these reactive groups are converted into nonin 15 minutes and held at thi temperature for minreactive groups, for example by reaction with suitable utes. 20 parts of a 10% aqueous acetic acid solution amino, hydroxy or thiol compounds or by replacement 30 are added and dyeing continued for 30 minutes at 100. with hydroxy groups (in the case of esters) or su C The wool is removed from the bath, rinsed with water acid groups. and dried. The scarlet dyeing obtained is fast to light,

As a rule the procedure used for the introduction of w hi g, perspiration nd milling. the acyl radical is to dissolve the dye in aqueous medium, if necessary with the addition of an organic solvent, such Example 2 as acetone, dioxan or pyridine, and then to add the acylatparts of the dye formed by tetrazotizing 4,4-diing agent at a low or higher temperature, if necessary amino-3,3-dirnethyl-1,l-diphenyl-6,6'-disulfonic acid and in presence of an acid-binding agent such as sodium hycoupling with 1-hydroxynaphthalene-4-sulfonic acid and droxide solution, sodium carbonate, sodium bicarbonate, l-aming-3-methylbenzene a dissolved in 530 arts of calcium hydroxide, calcium carbonate or pyridine which 40 water and 132 parts of pyridine. Chloroformic acid decyl at the same time may act as a catalyst. ester is added dropwise at 15-20" over the next 24 hours The introduction of a cyanuric radical is best carried ith vigorous ti i until h chromatogram of a out in aqu s medi m at about C- a at a WfiaklY acid ple shows that the starting dye is completely reacted. The reaction, at P values between 3 and The cyanuric reaction mass is acidified to a H value of 2.0 with about halide is employed as such in solid form or in solution in 20 parts of hydrochloric acid, and the precipitated dye all Organic Solvent, acetone- For the Primary 0011 is filtered oif and washed with parts of water. It is densation products of a cyanuric halide it is best to choose a temperature of 0 to C. and a pH-value of 3 to 7, for the secondary condensation products a temperature of 30 to 100 C. and a pH-value of 4 to 10, while for the di-, triand tetra-halogenopyrimidines temperatures berecrystallized by dissolving in 3000 parts of water and 120 parts of pyridine at with the subsequent addition of 200 parts of 25% sodium chloride solution, and 50 after cooling slowly to 5 in 5 hours it is filtered off,

tween and C are the most Suitable In the case Washed with 2% common salt solution, and dried at of the cyanuric halides, their Primary condensation W1th vacuum. The dye gives very brilliant scarlet shades nets and the di-, trior tetra-halogenopyrimidines, the W001 f FY wlllch P055655 e'XCeHeHt ifi to remaining exchangeable halogen atoms are exchanged for 55 hght, P P M1011, Washlng, and alkallne and acld mllllngamino, hydroxy or thiol groups which may be substituted. Exam l6 3 On completion of condensation or coupling the solution p or suspension may be neutralized if desired, and the final 18 parts of the dye on 1103's on; (IJH HOaS- CH3 4711;

dye is salted out with sodium or potassium chloride or 7 are dissolved in 176 parts of water and 44 parts of pyridine precipitated with acid, then filtered with suction, washed at 25. Chloroformic acid decyl ester is added dropwise and dried. for 24 hours at 1520 until the chromatogram of a sam- The dyes conforming to the invention are suitable, deple indicates that the starting dye is completely reacted. pending on their constitution, for the dyeing and print- The mass is acidified with hydrochloric acid and the preing of cellulosic fibers, wool, silk, leather and synthetic 75 cipitated dye filtered. Any excess of chloroformic acid 3,141,874a II 12 Example 38 Having thus disclosed the invention what We claim is: R is a member selected from the group consisting of 1. Water-soluble disazo dye of the formula hydrogen, lower alkyl and methoxy,

R is a member selected from the group consisting of R1 R3 R5 Ru 7 c hydrogen, methyl and methoxy, each of R and R being hydrogen when R5 is a member selected from a V 1 the group consisting of acetylamino, propionylamino R2 R4 R7 and butyrylamino, and D is a member selected from the group consisting of COX and co-o v, X being an aliphatic A is a radical selected from the group consisting of hydrocarbon radical with from 6 to 18 carbon atoms, l'chlofo f P y 3 Y Y Y- 20 and V being an aliphatic hydrocarbon radical with pyrazolyl, 1-(sulto)-phenyl-3-rnethyl-5-am1no-4-py- 1 y f 7 t 18 bon atom razolyl, and substituted naphthyl coupled in ortho- 2. A water-soluble disazo dye of the formula l l i l |N=N l|-1\I=1\1-| C ]--1 :noo 0)n-lwnz)Ken (I) (II) (III) position to a member selected fr m h g p wherein nuclei I and II are sulfonated, the total number R and R each is a member selected from the group consisting and 2 the Substituems of of sulfo groups in the two nuclei being 3, nuclei II and the P i naphthyl bemg sjelected from the III being methylated, the total number of methyl groups group cqnslstmgfif hydroxyg sulfo in each of said nuclei II and III being two, any further aceiylammo cmnamoilammo i i' substituent on nucleus I being Cl and there being no fur- :Eigg i g g g ig i g i z gif gg gg acry 40 ther substituents on nuclei II and III, the methyl groups p p y 0 a y on the latter being p-positioned relative to each other, n

consisting of hydrogen chloro methyl d s lf is a Whole number from 1 to 2 inclusive, and x is a whole R and R each is a member selected from the group number from 8 to 10 inclusive- R is a member selected from the group consisting 0 consisting of hydrogen, methyl and sulfo, 3. A Water-soluble disazo dye of the formula f 55 4. A water-soluble disazo dye of the formula (RH CH S'O H CH;

N=N- N=NONHCOO(CHZ)DCH3 S O H (3H hydrogen, methyl, methoxy, acetylamino, propionylamino and butyrylamino, 5. A water-soluble disazo dye of the formula OH om sio n JHE N=N--N=N--NHC OO(CH;)9CH;

E (EH e11 SOsH 13 m 6. A Water-soluble disazo dye of the formula (IXH (EH3 S!O3H $113 C1 SO H 0H 111 $0311 7. A water-soluble disazo dye of the formula (IJH S0311 ([3113 3 N=N N=N NHCO O OH,),CH, H03s SO H (11H;

References Cited in the file of this patent UNITED STATES PATENTS 2,402,538 Dreyfus June 25, 1946 

1. WATER-SOLUBLE DISAZO DYE OF THE FORMULA 